CN108434524A - A kind of antibacterial titanium preparation method with good biocompatibility of surface argentiferous - Google Patents
A kind of antibacterial titanium preparation method with good biocompatibility of surface argentiferous Download PDFInfo
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Abstract
The invention discloses a kind of antibacterial titanium preparation methods with good biocompatibility of surface argentiferous, which is characterized in that includes the following steps：First by anodizing in the uniform titania nanotube of titanium surface construction, as the reservoir of silver nano-grain；Secondly, sodium alginate aoxidized using sodium metaperiodate to obtain dialdehyde sodium alginate, it is denoted as ADA, as anionic polyelectrolyte, LBL self-assembly, which is carried out, with cationic polyelectrolyte CHI forms polyelectrolyte multilayer film, the driving force that the multilayer film is formed comes from the covalent interaction of the electrostatic interaction of ADA and CHI and the amino on the aldehyde radical and CHI on ADA, the multilayer film of the stabilization of structure is set to efficiently control the release of silver ion, reduce silver ion toxicity caused by osteoblast, realize good biocompatibility, and excellent anti-microbial property can be realized to assign the good antibacterial of titanium-based implant and bone formation performance.
Description
Technical field
The present invention relates to Material Field, the antibacterial titanium system with good biocompatibility of specifically a kind of surface argentiferous
Preparation Method.
Background technology
Titanium or titanium alloy has excellent mechanical strength, biocompatibility and corrosion resistance, is dentistry and orthopaedics therapy
In most common biomaterial.However, the relevant postoperative infection of biomaterial is still one of band with clinical application important
Challenge.Implantation postoperative infection can lead to the healing delay of wound, or even need to carry out operation repeatedly, this can lead to the pain of patient
And excessive expense.More seriously, bacterium is once attached to implantation titanium surface, they can be resisted by forming biomembrane
Carry out the lethal action of self-immunity systems, while antibiosis extract for treating is very low to the killing-efficiency for having formed the bacterium of biomembrane.Research
Show that the Attachment (4-6 hours) of bacterium is inhibited to be proved to be to inhibit one step of key of biofilm formation.
Based on this problem, researchers increasingly pay attention to assigning titanium-based implantation material anti-infection ability, such as in titanium
Surface combination antibiotic, silver nano-grain, antibacterial peptide etc..In recent years, silver-colored (silver) sill, especially Nano silver grain, by
In its broad-spectrum antiseptic, antimycotic and antiviral activity, every field has been widely used in it.
In addition researcher's discovery, silver nano-grain and antibiotic are used in combination to drug-fast bacteria MRSA and kerekou pneumonia primary
Bacterium has apparent inhibiting effect.It has been recognized that the antibacterial action of Nano silver grain is the silver released by Nano silver grain
(Ag) ion and it is non-particulate caused by itself.Generally, it is considered that Ag ions are cell compatibilities in low concentration.However, short
A large amount of Ag is released in time can cause cytotoxicity.
Based on the above, bio-modification is carried out to the titanium base material surface of designed silver-containing nanoparticles, in addition to energy
The slow release effect for enough realizing effective silver ion while imparting titanium base material effective anti-microbial property and is realized good thin
Born of the same parents' compatibility is current urgent problem to be solved.
Invention content
Present invention aim to address problems of the prior art, provide a kind of surface argentiferous has good biological
The antibacterial titanium preparation method of compatibility.
To realize the present invention purpose and the technical solution adopted is that such, a kind of surface argentiferous has good biological phase
The antibacterial titanium preparation method of capacitive, which is characterized in that include the following steps：
1) titania nanotube for being loaded with silver nano-grain is prepared
1.1) after processing being dried in the titanium foil after cleaning, then electrochemical corrosion course is carried out；
In the drying process：Temperature range is 40~80 DEG C, and the time is 2~6 hours；
In the electrochemical corrosion course：Using platinum foil as cathode, using the titanium foil after drying process as anode；It is electrolysed molten
Liquid is the mixture of the water containing ammonium fluoride and/or glycerine；
A concentration of 0.27M of the ammonium fluoride；
The volume ratio of the water and glycerine includes 0 ︰ 1,1 ︰ 3,1 ︰ 1,3 ︰ 1 or 1 ︰ 0；
In the electrochemical corrosion course：Constant voltage is 10~30V, and electrolysis time is 30~90 minutes；
1.2) titanium foil after the electrolysis obtained in step 1.1) is calcined, obtains the Detitanium-ore-type dioxy of stable structure
Change titanium nanotube；
In the calcination process：Calcination temperature is 450 DEG C；Calcination time is 2 hours；
1.3) anatase type titanium dioxide nano tube obtained in step 1.2) is immersed in silver nitrate solution, after taking-up
Be rinsed using phosphate buffered saline solution, finally by the anatase type titanium dioxide nano tube after flushing be placed under ultraviolet lamp into
The ultraviolet reduction of row, obtains the titania nanotube for being loaded with silver nano-grain；
In the soaking process：A concentration of 0.01~1M of silver nitrate solution, soaking time are 2~12 hours；
In the ultraviolet reduction process：Recovery time is 10~60 minutes；
2) oxidized sodium alginate is prepared
2.1) under conditions of room temperature is protected from light, sodium metaperiodate is added in mixture A, magnetic agitation is after 6~24 hours,
Obtain product A；
The mixture A is sodium alginate water and/or alcohol mixed solution；The concentration of sodium alginate in the mixture A
It is 1%~5%；0~0 ︰ 5 of ranging from 5 ︰ of the volume ratio of the water and ethyl alcohol；
The molar ratio of the sodium metaperiodate and sodium alginate is 0.1 ︰, 1~1 ︰ 1；
2.2) after ethylene glycol is added in the product A obtained in step 2.1), sodium chloride is added, product B is obtained；
The volume of the ethylene glycol is 1~10mL, and the weight of the sodium chloride is 1~5g；
2.3) ethyl alcohol will be added in the product B obtained in step 2.2), standing makes its natural subsidence, then carries out centrifuging
Cheng Hou collects sediment；
The volume of the ethyl alcohol is 200~800mL, and the time of the standing is 30~90 minutes；
2.4) sediment obtained in step 2.3) is placed in distilled water, adds ethyl alcohol, is precipitated again, stood
Make its natural subsidence, after then carrying out centrifugal process, collects sediment；
The volume of the distilled water is 100~300mL, and the volume of the ethyl alcohol is 200~800mL, the standing when
Between be 30~90 minutes；
After the step 2.4) repeats 3~5 times, product C is obtained；
2.5) the product C obtained in step 2.4) is dialysed in distilled water in liquid with bag filter, after freeze-drying,
Collection obtains product oxidized sodium alginate；
The time of the dialysis procedure is 3 days, and distilled water is replaced daily in the dialysis procedure；
In the freezing dry process：Temperature is -55 DEG C, and the time is 2 days；
3) in the titania nanotube surface construction polyelectrolyte multilayer film of load silver nano-grain
3.1) oxidized sodium alginate obtained in step 2.5) is dissolved in the sterile distilled water in container A, obtains oxygen
Change sodium alginate soln；A concentration of 1~5mg/mL of the oxidized sodium alginate solution；
It dissolves chitosan in again in the sterile distilled water in container B, obtains chitosan solution, gathered shell by glacial acetic acid
The pH value of sugar juice is adjusted to 5.5；A concentration of 1~5mg/mL of the chitosan solution；
3.2) by the chitosan solution after the oxidized sodium alginate solution obtained in step 3.1) and adjusting pH value, in step
1) being loaded on the titania nanotube of silver nano-grain for being obtained in carries out alternately spin coating 5~15 times, obtains in titanium table
Antibacterial interface of the face structure with the release of control silver ion and with good biocompatibility.
Further, the cleaning process in the step 1.1) is：Titanium foil is used into ethyl alcohol, acetone, ethyl alcohol and distilled water successively
Each self-cleaning 10~20 minutes.
Further, the speed range of magnetic agitation is 500 revs/min~2000 revs/min of rotating speed in the step 2.1).
Further, the rate of centrifugal process is 5000~10000 revs/min in the step 2.3), and the time is 5~20 points
Clock.
Further, the rate of centrifugal process is 5000~10000 revs/min in the step 2.4), and the time is 5~20 points
Clock.
Further, the molecular weight of the bag filter in the step 2.5) is 3500D.
Further, spin coating instrument is used in the spin coating process in the step 3.1), the setting of the spin coating instrument includes：Turn
Speed is 100~400rpm/min, and the time is 5~10s；Rotating speed is 2000~4000rpm/min, and the time is 20~60s.
A kind of surface argentiferous obtained by claim 1~7 any one of them preparation method has good biological
The antibacterial titanium of compatibility.
It is worth noting that：In recent years, the material of the nano particle of silver-based antimicrobial material, especially argentiferous is based in biology
Material Field receives more and more attention, but the violent release of silver ion in vivo at the beginning may make in silver-based material
At cell and tissue toxicity.Therefore, by various method of modifying, the violent release to control silver ion is significantly.Research
Show the method by microwave radiation technology, forms the shell structure of tea polyphenols on silver nano-grain surface, can effectively control silver ion
Release, and have effective anti-microbial property, while will not to mammalian cell generate cytotoxicity.
In addition, due to its simplicity, versatility, controllability and low cost, layer-by-layer has been applied in shaping
In the preparation of the application function coating of surgery.In addition, more using the polyelectrolyte of layer-by-layer structure on titanium surface
The slow releasing function in the loaded functional ionic/drug in titanium surface may be implemented, for example, by BMP in tunic2It is loaded as intercalation
Into gelatin/chitosan polyelectrolyte multilayer film；Zinc ion is loaded into gelatin/chitosan polyelectrolyte multilayer film.Here
The driving force for being formed by polyelectrolyte multilayer film is mainly the electrostatic phase by cationic polyelectrolyte and anionic polyelectrolyte
Interaction (electrostatic interaction) is formed by.
In this research, by electrochemistry anodic oxidation in the uniform Nano tube array of titanium dioxide of titanium surface construction
(TNT), and as drug reservoir, silver nano-grain is loaded into nanotube (TNT-Ag).Then, with sodium metaperiodate oxygen
Change sodium alginate and obtain dialdehyde sodium alginate, is named as ADA.Using CHI and ADA as polycation and polyanion, simultaneously
There is abundant amino (- NH on CHI2), there is abundant aldehyde radical (- CHO) to be loaded by layer-by-layer on ADA
The titania nanotube surface construction polyelectrolyte multilayer film of silver nano-grain.The driving force that multilayer film is formed comes from
The aldehyde radical on amino and ADA in the electrostatic interaction (electrostatic interaction) and CHI of CHI and ADA
By formed schiff bases covalent interaction (covalent assembly interaction).
Carry out following supposition：It drives to be formed under acting at two kinds due to polyelectrolyte multilayer film, so in physiologic ring
The stability of the film formed under border can be stronger, can more effectively realize the control release of silver ion.Meanwhile by due to good
Biocompatibility, CHI and ADA LBL self-assemblies structure polyelectrolyte multilayer film the sustained release of loaded drug may be implemented simultaneously
Assign titanium-based implant biological function.
Therefore, more in the CHI/ADA of the titania nanotube surface construction of silver nano-grain load in present study
Tunic is formed by then passing through under two kinds of urging forces of electrostatic interaction and covalent interaction, has stronger stability,
The control release that can effectively realize silver ion, cytotoxicity is not caused while realizing effective antibacterial ability again.
The solution have the advantages that unquestionable, the present invention has the following advantages：
1) preparation method in the present invention does not need special installation, easy to operate, controllability is strong.
2) present invention is controlled using the antibacterial titanium with good biocompatibility of the argentiferous of this method structure with effective
The violent release of the early stage of silver ion processed, while there is good biocompatibility, there is important grind in the application of bone grafting material
Study carefully value and clinical meaning.
Description of the drawings
Fig. 1 is the surface scan electron microscope of three kinds of different materials and loads the titania nanotube of silver nano-grain
Transmission electron microscope picture；
The Fourier transform infrared spectroscopy figure of dialdehyde sodium alginates of the Fig. 2 for sodium alginate and after aoxidizing；
Fig. 3 is the surface water contact angle of three kinds of different materials；
Fig. 4 is releasing curve diagram of the silver ion in 28 days in TNT-Ag the and LBL samples in phosphate buffer；
Fig. 5 is lactic dehydrogenase enzyme r e lease content situation of the osteoblast in different materials；
Fig. 6 is cell activity figure of the different modifying sample surfaces osteoblasts cultivation after 4 days and 7 days；
Fig. 7 is nucleus and cytoskeleton colored graph of the different modifying sample surfaces osteoblasts cultivation after 2 days；
Fig. 8 is the adherency situation after different modifying sample surfaces staphylococcus aureus and Escherichia coli are cultivated 6 hours
(CLSM) figure；
Fig. 9 is the material surface after different modifying sample surfaces staphylococcus aureus and Escherichia coli are cultivated 6 hours
Bacteriostasis rate situation map；
Figure 10 is thin after different modifying sample surfaces staphylococcus aureus and Escherichia coli are cultivated 6,12 and 24 hours
Bacterium activity figure (mtt assay).
In Fig. 1：Fig. 1 a are the surface scan electron microscope of titania nanotube (TNT)；Fig. 1 b are silver-carrying nano particle
Titania nanotube (TNT-Ag) surface scan electron microscope；Fig. 1 c are (CHI/ADA)5It sweeps on the surface of plastic film mulch sample LBL
Retouch electron microscope；Fig. 1 d are the transmission electron microscope picture of the titania nanotube (TNT-Ag) of silver-carrying nano particle；
In fig. 2：Fig. 2 a are the Fourier transform infrared spectroscopy figure of sodium alginate；Fig. 2 b are the dialdehyde seaweed after oxidation
The Fourier transform infrared spectroscopy figure of sour sodium；
In the figure 7：Fig. 7 a are adherency figure of the osteoblast behind surfaces TNT 2 days；Fig. 7 b are osteoblast in TNT-Ag tables
Adherency figure of the face after 2 days；Fig. 7 c are adherency figure of the osteoblast behind surfaces LBL 2 days；
In fig. 8：The bacterium that Fig. 8 a and 8d are respectively staphylococcus aureus and Escherichia coli behind surfaces TNT 6 hours
Adherency figure；The bacterial adhesion figure that Fig. 8 b and 8e are respectively staphylococcus aureus and Escherichia coli behind surfaces TNT-Ag 6 hours；
The bacterial adhesion figure that Fig. 8 c and 8f are respectively staphylococcus aureus and Escherichia coli behind surfaces LBL 6 hours.
Specific implementation mode
With reference to embodiment, the invention will be further described, but should not be construed the above-mentioned subject area of the present invention only
It is limited to following embodiments.Without departing from the idea case in the present invention described above, according to ordinary skill knowledge and used
With means, various replacements and change are made, should all include within the scope of the present invention.
Embodiment 1：
A kind of antibacterial titanium preparation method with good biocompatibility of surface argentiferous, which is characterized in that including with
Lower step：
1) Nano tube array of titanium dioxide (TNT) for being 70nm using anodizing structure caliber on titanium surface, will
It is immersed in silver nitrate solution, and silver nano-grain is loaded in titania nanotube by the method for ultraviolet reduction
(TNT-Ag)。
1.1) after processing being dried in the titanium foil (10mm × 10mm) after cleaning, then electrochemical corrosion course is carried out；
The cleaning process is：Titanium foil is used into ethyl alcohol, acetone, ethyl alcohol and each self-cleaning of distilled water 15 minutes successively.
In the drying process：Temperature is 60 DEG C, and the time is 4 hours；
In the electrochemical corrosion course：Using platinum foil as cathode, using the titanium foil after drying process as anode；It is electrolysed molten
Liquid is the mixture of the water containing ammonium fluoride and/or glycerine；
A concentration of 0.27M of the ammonium fluoride；
The volume ratio of the water and glycerine includes 1 ︰ 1；
In the electrochemical corrosion course：Constant voltage is 20V, and electrolysis time is 60 minutes；
1.2) titanium foil after the electrolysis obtained in step 1.1) is calcined, obtains the Detitanium-ore-type dioxy of stable structure
Change titanium nanotube, is denoted as TNT；
In the calcination process：Calcination temperature is 450 DEG C；Calcination time is 2 hours；
1.3) anatase type titanium dioxide nano tube obtained in step 1.2) is immersed in silver nitrate solution, after taking-up
Be rinsed using phosphate buffered saline solution, finally by the anatase type titanium dioxide nano tube after flushing be placed under ultraviolet lamp into
The ultraviolet reduction of row, obtains the titania nanotube for being loaded with silver nano-grain, is denoted as TNT-Ag；
In the soaking process：A concentration of 0.5M of silver nitrate solution, soaking time are 2 hours；
In the ultraviolet reduction process：Recovery time is 30 minutes；
2) oxidized sodium alginate (ADA) is prepared；
2.1) under conditions of room temperature is protected from light, sodium metaperiodate is added in mixture A, magnetic agitation obtains after 24 hours
To product A；
The rate of the magnetic agitation is 1000 revs/min；
The mixture A is sodium alginate water and/or alcohol mixed solution；The concentration of sodium alginate in the mixture A
It is 5%；The volume ratio of the water and ethyl alcohol includes 4 ︰ 1；
The molar ratio of the sodium metaperiodate and sodium alginate is 1 ︰ 1；
2.2) after ethylene glycol is added in the product A obtained in step 2.1), sodium chloride is added, product B is obtained；
The volume of the ethylene glycol is 10mL, and the weight of the sodium chloride is 5g；
2.3) ethyl alcohol will be added in the product B obtained in step 2.2), standing makes its natural subsidence, then carries out centrifuging
Cheng Hou collects sediment；
The volume of the ethyl alcohol is 800mL, and the time of the standing is 60 minutes, and rotating speed is in the centrifugal process
10000 revs/min, the time is 10 minutes；
2.4) sediment obtained in step 2.3) being placed in distilled water, adds ethyl alcohol, standing makes its natural subsidence,
Then after carrying out centrifugal process, sediment is collected, is precipitated again；
The volume of the distilled water is 100mL, and the volume of the ethyl alcohol is 600mL, and the time of the standing is 60 minutes,
Rotating speed is 10000 revs/min in the centrifugal process, and the time is 10 minutes；
After the step 2.4) repetition step carries out 3~5 times, product C is obtained；
2.5) the product C obtained in step 2.4) is dialysed in distilled water in liquid with bag filter, after freeze-drying,
Collection obtains product oxidized sodium alginate；
The time of the dialysis procedure is 3 days, and distilled water is replaced daily in the dialysis procedure；
In the freezing dry process：Temperature is -55 DEG C, and the time is 2 days；
The molecular weight of the bag filter is 3500D；
3) in the titania nanotube surface construction polyelectrolyte multilayer film of load silver nano-grain
3.1) oxidized sodium alginate obtained in step 2.5) is dissolved in the sterile distilled water in container A, obtains oxygen
Change sodium alginate soln；A concentration of 5mg/mL of the oxidized sodium alginate solution；
It dissolves chitosan in again in the sterile distilled water in container B, obtains chitosan solution, gathered shell by glacial acetic acid
The pH value of sugar juice is adjusted to 5.5；A concentration of 5mg/mL of the chitosan solution；
3.2) by the chitosan solution after the oxidized sodium alginate solution obtained in step 3.1) and adjusting pH value, in step
1) being loaded on the titania nanotube of silver nano-grain for being obtained in carries out alternately spin coating 5 times, obtains in titanium surface structure
The antibacterial interface with the release of control silver ion and with good biocompatibility is built, LBL is denoted as.
Spin coating instrument is used in the spin coating process, the setting of the spin coating instrument includes：Rotating speed is 300rpm/min, time
For 8s；Rotating speed is 3000rpm/min, time 40s.
In Fig. 1：
Fig. 1 a are the surface scan electron microscope of titania nanotube (TNT)；Two specifically obtained after the completion of step 1)
The scanning electron microscope (SEM) photograph of titanium oxide nanotubes；There is uniform pipe by the nanotube being prepared in visible the present embodiment in Fig. 1 a
Diameter, and be distributed in 70nm or so；
Fig. 1 b are the surface scan electron microscope of the titania nanotube (TNT-Ag) of silver-carrying nano particle；It can from Fig. 1 b
It is successfully loaded into nanotube by ultraviolet reduction silver nano-grain with finding out, and the grain size of silver nano-grain is on the left sides 20nm
It is right；
Fig. 1 c are (CHI/ADA)5The surface scan electron microscope of plastic film mulch sample LBL；The nanometer after caning be found that plastic film mulch in figure
Pipe is successfully covered；
Fig. 1 d are the transmission electron microscope picture of the titania nanotube (TNT-Ag) of silver-carrying nano particle.
The Fourier transform infrared spectroscopy figure of dialdehyde sodium alginates of the Fig. 2 for sodium alginate and after aoxidizing；
Fig. 2 is the Fourier transform infrared spectroscopy figure that products therefrom ADA is prepared in step 2), as a result, it has been found that
1677.7cm-1There is the absorption peak for belonging to aldehyde carbonyl groups in place, it was demonstrated that forms dialdehyde sodium alginate after oxidation.
Fig. 3 is the surface water contact angle of three kinds of different materials；The water contact angle on the surfaces TNT formed after anodic oxidation is
21.8°；The water contact angle of TNT-Ag sample surfaces is reduced to 16.5 °, this is because the change of the topological structure on surface；Layer by layer certainly
It assembles the LBL samples water contact angle formed later and rises to 37.8 ° again.
By the above it can be proved that present invention success has good biological phase in a kind of argentiferous of titanium surface construction
The antibacterial interface of capacitive.
It is worth noting that：The present embodiment is first by electrochemical anodic oxidation in the uniform titanium dioxide of titanium surface construction
Titanium nano-tube array, and load silver nano-grain as reservoir；Then richness is obtained by sodium periodate oxidation sodium alginate
Dialdehyde sodium alginate (ADA) containing aldehyde radical；Finally use ADA and CHI as anionic polyelectrolyte and cationic polyelectrolyte,
Using layer-by-layer load silver nano-grain nanotube surface construct by electrostatic interaction and covalently mutually
Two kinds of urging forces of effect are formed by stable polyelectrolyte multilayer film, and the early stage that multilayer film can effectively control silver ion is sudden and violent
It releases, there is good biocompatibility, while effectively antibacterial action can be played.
In building flow, factors can influence the synthesis of titania nanotube, the load of silver nano-grain and
The structure of titanium surface polyelectrolyte multilayer film, such as the oxidation of the concentration of silver nitrate, Ultraviolet Oxidation time, sodium alginate are imitated
In rate, electrolytic process electrolyte/voltage and when electrolysis time, LBL self-assembly gather the rotating speed of the concentration spin coating of male/female ion with
Time etc., different control conditions will influence the structure at antibacterial titanium interface.
The present embodiment is focused on the screening to the oxidation efficiency, silver nitrate concentration of sodium alginate, is gathered during LBL self-assembly
The rotating speed that the concentration of male/female ion, spin coating use is investigated.The results show that when rubbing with sodium metaperiodate and sodium alginate
You are than being 1 ︰ 1, you can obtains the ADA products with good cell compatibility；And a concentration of 0.5M when silver nitrate, it is ultraviolet to go back
When the former time is 30 minutes, you can obtain the silver nano-grain with good anti-microbial property；When spin coating is set as 300rpm
When the concentration of (8s), 3000rpm (40s), Chi-c and HA-c are respectively 2mg/mL and 2mg/mL, the shell ADA/CHI of 5 cycles
Uniform coating can be formed in the nanotube surface of silver-carrying nano particle.
Experimental example 1：
The release of silver ion, the evaluation of the biocompatibility of material
In this experimental example, two kinds of different sample TNT-Ag and LBL samples are immersed in Phosphorylation Buffer (PBS) and are used to
The release conditions of silver ion in research material；And LDH of the evaluation osteoblast on different materials surface is horizontal, cell activity and
Cell adherence situation, specifically includes following steps：
1) in order to verify the influence that multilayer film discharges silver ion, every group (TNT-Ag and LBL) 5 samples are dipped into respectively
In 5mL PBS；
After different time is incubated (37 DEG C) in (1,4,7,14,28 day), take 5mL leachates to detect silver ion in every group of sample
Rate of release.
The burst size of silver ion is obtained using ICP-AES measurements in this experiment；
No matter figure 4, it is seen that at which, the silver ion that LBL samples release is below TNT-Ag samples at time point
Product, therefore the polyelectrolyte multilayer film constructed by us can limitedly control the release of silver ion.
2) Fig. 5 is that lactic dehydrogenase (LDH) of the osteoblast in different materials discharges content situation；
When osteoblast grows to the third generation, 2 × 104The density in a/hole is inoculated on each titanium plate surface and TCPS,
37 DEG C, cultivate different time under the conditions of 5%CO2, during which do not change liquid；Skeletonization after cultivating 3 days is had detected using LDH detection kits
LDH of the cell on different materials surface is horizontal.
As shown in the result in Fig. 5, it is higher than other to LDH burst size equal conspicuousness of the osteoblast in TNT-Ag samples
Group (0.05 or 0.01 is horizontal) illustrates that the Ag ions that TNT-Ag sample early stages release produce cytotoxicity, and is using
(ADA/CHI) release for controlling silver ion of conspicuousness after 5 multilayer films block, to reduce the cytotoxicity of early stage.
3) Fig. 6 is cell activity figure of the different modifying sample surfaces osteoblasts cultivation after 4 days and 7 days；
When osteoblast grows to the third generation, 2 × 104The density in a/hole is inoculated on each titanium plate surface and TCPS,
37 DEG C, cultivate different time under the conditions of 5%CO2, change the liquid once within every two days；It is had detected 4 days and 7 days and is cultivated using CCK-8 technologies
The cell activity on different materials surface afterwards, in different time points, in order to detect the osteoblast cells activity on different materials surface,
It inhales and fresh culture and 20 μ LCCK-8 solution that 200 μ L are free of serum is added after abandoning old culture solution in each hole, continue to cultivate
Each group light absorption value is measured after 1.5h at 450nm.
As shown in the result in Fig. 6, no matter at 4 days or 7 days, the equal conspicuousness of cell activity of TNT-Ag samples it is less than
TNT and LBL prints；Although at 7 days, cell activity of the osteoblast on LBL samples is less than TNT samples, and there is no notable
Sex differernce；So our (ADA/CHI) 5 polyelectrolyte multilayer films constructed by TNT-Ag sample surfaces, have good thin
Born of the same parents' compatibility.
4) Fig. 7 is nucleus and cytoskeleton colored graph of the different modifying sample surfaces osteoblasts cultivation after 2 days；
When osteoblast grows to the third generation, the density in 8000/hole is inoculated in each titanium substrate surface, stationary culture 2
It, is incubated osteoblast 15 minutes with 0.4% tritonX-100 and punches, with being incubated in 4 DEG C of refrigerators of the phalloidine configured
Overnight to dye the skeleton of osteocyte；Then osteocyte nucleus 5min is dyed using Hochest33258, it is aobvious being inverted fluorescence
Micro- microscopic observation osteoblast adheres to situation.
Such as the osteoblast coloration result in Fig. 7, it has been found that in TNT and TNT-Ag sample surfaces, osteoblast glues
Attached quantity is less than on LBL samples；And the osteoblast on TNT-Ag samples shows poor situation of sprawling, and
Osteoblast on LBL samples shows more cell pseudopodium, implies good adherency situation, is attributed to constructed multilayer
The good biocompatibility of film.
It is found that the release for the silver ion that multilayer film prepared in the present invention can be controlled effectively in from the discussion above, from
And silver ion toxicity caused by osteoblast is reduced, to realize good cell compatibility.
Experimental example 2：
Material surface bacterial adhesion, bacteriostasis rate and bacterial activity detection
By the staphylococcus aureus diluted and Escherichia coli respectively with 1 × 106The density in a/hole is inoculated in not
With material surface, after cultivate 6 hours under the conditions of 37 DEG C, utilize the nucleoid 5min using Hochest33258 dye bacteriums；In addition
Also have detected bacteriostasis rate of the different materials surface relative to pure titanium surface after cultivating 6 hours.
1) in the detection, sample is observed in order to prepare CLSM, first with 4% paraformaldehyde solution under the conditions of 4 DEG C
The fixation that 30 minutes are carried out to bacterium, then carries out it nucleoid 5min that Hochest33258 contaminates bacterium under the conditions of 4 DEG C, so
CLSM observes the bacterial adhesion situation on different materials surface afterwards；
2) in order to detect the anti-bacterial attachment efficiency on different materials surface, different titaniums is taken out, is gently rushed with PBS
It washes 3 times and washes off nonadherent bacterium, 1mlPBS is then added and ultrasound makes the bacterium of adherency split away off, then draws 50 μ L and exists
It carries out painting tablet on MHB solid mediums, different groups of bacterium colony number is counted under the conditions of 37 DEG C after culture 18h, finally with pure titanium
Surface calculates bacteriostasis rate as a control group；
3) in order to detect the bacterial activity of different materials surface adhesion bacterium, have detected 6 using mtt assay, 12, cultivate for 24 hours
The bacterial activity on different materials surface afterwards, in different time points, in order to detect the bacterial activity on different materials surface, old training is abandoned in suction
The MHB culture mediums and 20 μ LMTT mother liquor solutions of 200 μ L is added after nutrient solution in each hole, continues after cultivating 6h, is dissolved with DMSO purple
Color crystallizes, and each group light absorption value is measured at 490nm.
Fig. 8 is the adherency situation after different modifying sample surfaces staphylococcus aureus and Escherichia coli are cultivated 6 hours
(CLSM) figure；
Illustrate the CLSM figures of different materials surface adhesion bacterium after cultivating in fig. 86 hours.We can be with from figure
See after cultivating 6h, whether staphylococcus aureus or Escherichia coli, almost without bacterium on TNT-Ag and LBL samples
Adherency, illustrates, in both material surfaces, due to the release of silver ion, excellent anti-bacterial attachment can be shown in early stage
Ability.
Fig. 9 is the material surface after different modifying sample surfaces staphylococcus aureus and Escherichia coli are cultivated 6 hours
Bacteriostasis rate situation map；
The antibacterial efficiency of two kinds of different materials surface pair bacterium after cultivating 6 hours is illustrated in fig.9；In 6h, TNT-
Ag and LBL material surfaces have reached 90% or more to the bacteriostasis rate of staphylococcus aureus and Escherichia coli.
Figure 10 is thin after different modifying sample surfaces staphylococcus aureus and Escherichia coli are cultivated 6,12 and 24 hours
Bacterium activity figure (mtt assay)；
The bacterial activity on the different materials surface after different incubation times is shown in Fig. 10, there it can be seen that
Though at which at time point, the staphylococcus aureus of TNT-Ag and LBL sample surfaces and the bacterial activity of Escherichia coli pole
It is less than TNT groups to conspicuousness.
Thus, the results showed that compared to TNT groups, the sample (TNT-Ag and LBL groups) of silver-containing nanoparticles can be realized effectively
Anti-microbial property.
It is easy to operate, controllability is strong in conclusion the preparation method in the present invention does not need special installation；Institute of the present invention
The polyelectrolyte multilayer film of structure can not only efficiently control the release of silver ion, show good biocompatibility, and
It can realize effective antibacterial ability, there is important researching value and clinical meaning in the application of antibacterial bone grafting material.
Claims (8)
1. a kind of antibacterial titanium preparation method with good biocompatibility of surface argentiferous, which is characterized in that including following
Step：
1) titania nanotube for being loaded with silver nano-grain is prepared
1.1) after processing being dried in the titanium foil after cleaning, then electrochemical corrosion course is carried out；
In the drying process：Temperature range is 40~80 DEG C, and the time is 2~6 hours；
In the electrochemical corrosion course：Using platinum foil as cathode, using the titanium foil after drying process as anode；Electrolytic solution is
The mixture of water and/or glycerine containing ammonium fluoride；
A concentration of 0.27M of the ammonium fluoride；
The volume ratio of the water and glycerine includes 0 ︰ 1,1 ︰ 3,1 ︰ 1,3 ︰ 1 or 1 ︰ 0；
In the electrochemical corrosion course：Constant voltage is 10~30V, and electrolysis time is 30~90 minutes；
1.2) titanium foil after the electrolysis obtained in step 1.1) is calcined, obtains the anatase titanium dioxide of stable structure
Nanotube；
In the calcination process：Calcination temperature is 450 DEG C；Calcination time is 2 hours；
1.3) anatase type titanium dioxide nano tube obtained in step 1.2) is immersed in silver nitrate solution, is used after taking-up
Phosphate buffered saline solution is rinsed, and finally the anatase type titanium dioxide nano tube after flushing is placed under ultraviolet lamp and carries out purple
Outer reduction obtains the titania nanotube for being loaded with silver nano-grain；
In the soaking process：A concentration of 0.01~1M of silver nitrate solution, soaking time are 2~12 hours；
In the ultraviolet reduction process：Recovery time is 10~60 minutes；
2) oxidized sodium alginate is prepared
2.1) under conditions of room temperature is protected from light, sodium metaperiodate is added in mixture A, magnetic agitation obtains after 6~24 hours
Product A；
The mixture A is sodium alginate water and/or alcohol mixed solution；A concentration of the 1% of sodium alginate in the mixture A
~5%；0~0 ︰ 5 of ranging from 5 ︰ of the volume ratio of the water and ethyl alcohol；
The molar ratio of the sodium metaperiodate and sodium alginate is 0.1 ︰, 1~1 ︰ 1；
2.2) after ethylene glycol is added in the product A obtained in step 2.1), sodium chloride is added, product B is obtained；
The volume of the ethylene glycol is 1~10mL, and the weight of the sodium chloride is 1~5g；
2.3) ethyl alcohol will be added in the product B obtained in step 2.2), standing makes its natural subsidence, then carries out centrifugal process
Afterwards, sediment is collected；
The volume of the ethyl alcohol is 200~800mL, and the time of the standing is 30~90 minutes；
2.4) sediment obtained in step 2.3) is placed in distilled water, adds ethyl alcohol, is precipitated again, standing makes it
Natural subsidence after then carrying out centrifugal process, collects sediment；
The volume of the distilled water is 100~300mL, and the volume of the ethyl alcohol is 200~800mL, and the time of the standing is
30~90 minutes；
After the step 2.4) repeats 3~5 times, product C is obtained；
2.5) the product C obtained in step 2.4) is dialysed in distilled water in liquid with bag filter, after freeze-drying, is collected
Obtain product oxidized sodium alginate；
The time of the dialysis procedure is 3 days, and distilled water is replaced daily in the dialysis procedure；
In the freezing dry process：Temperature is -55 DEG C, and the time is 2 days；
3) in the titania nanotube surface construction polyelectrolyte multilayer film of load silver nano-grain
3.1) oxidized sodium alginate obtained in step 2.5) is dissolved in the sterile distilled water in container A, obtains oxidation sea
Solution of sodium alginate；A concentration of 1~5mg/mL of the oxidized sodium alginate solution；
It dissolves chitosan in again in the sterile distilled water in container B, obtains chitosan solution, it is by glacial acetic acid that chitosan is molten
The pH value of liquid is adjusted to 5.5；A concentration of 1~5mg/mL of the chitosan solution；
3.2) by the chitosan solution after the oxidized sodium alginate solution obtained in step 3.1) and adjusting pH value, in step 1)
Being loaded on the titania nanotube of silver nano-grain for obtaining carries out alternately spin coating 5~15 times, obtains in titanium surface structure
Build the antibacterial interface with the release of control silver ion and with good biocompatibility.
2. a kind of antibacterial titanium preparation method with good biocompatibility of surface argentiferous according to claim 1,
It is characterized in that：Cleaning process in the step 1.1) is：Titanium foil is used into ethyl alcohol, acetone, ethyl alcohol and distilled water respectively successively
Cleaning 10~20 minutes.
3. a kind of antibacterial titanium preparation method with good biocompatibility of surface argentiferous according to claim 1,
It is characterized in that：The speed range of magnetic agitation is 500 revs/min~2000 revs/min of rotating speed in the step 2.1).
4. a kind of antibacterial titanium preparation method with good biocompatibility of surface argentiferous according to claim 1,
It is characterized in that：The rate of centrifugal process is 5000~10000 revs/min in the step 2.3), and the time is 5~20 minutes.
5. a kind of antibacterial titanium preparation method with good biocompatibility of surface argentiferous according to claim 1,
It is characterized in that：The rate of centrifugal process is 5000~10000 revs/min in the step 2.4), and the time is 5~20 minutes.
6. a kind of antibacterial titanium preparation method with good biocompatibility of surface argentiferous according to claim 1,
It is characterized in that：The molecular weight of bag filter in the step 2.5) is 3500D.
7. a kind of antibacterial titanium preparation method with good biocompatibility of surface argentiferous according to claim 1,
It is characterized in that：Spin coating instrument is used in spin coating process in the step 3.1), the setting of the spin coating instrument includes：Rotating speed is
100~400rpm/min, time are 5~10s；Rotating speed is 2000~4000rpm/min, and the time is 20~60s.
8. a kind of surface argentiferous obtained by claim 1~7 any one of them preparation method has good biological phase
The antibacterial titanium of capacitive.
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